Ordered polyacetylenes and process for the preparation thereof

ABSTRACT

Polyacetylene compounds and process for the preparation thereof from a chiral dihydroxy amide are described. The compounds preferably have diacyl groups attached to the amide. The compounds are useful for making films which are electrically conductive, near infrared absorbing, polarizing, and have the optical characteristic and other properties of polyacetylenes.

This application is a division of Ser. No. 09/273,219 filed Mar. 19,1999, now U.S. Pat. No. 6,194,529.

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT

This invention was supported by National Science Foundation Grant NumberIBN 9507189. The U.S. government has certain rights in this invention.

CROSS-REFERENCE TO RELATED APPLICATION

None.

BACKGROUND OF THE INVENTION

(1) Field of the Invention

The present invention relates to novel ordered polyacetylene compoundswith side-by-side carbon chains and aligned acetylene groups in eachchain and to a process for the preparation thereof. In particular, thepresent invention preferably relates to polydiacetylene compounds withtwo adjacent acetylene groups in each chain.

(2) Description of Related Art

Diacetylenes polymerize to give systems with electrical and opticalproperties that can potentially be exploited for a variety of importantapplications. These include conductive devices, electrochromic devicesand biosensors. In order for polymerization to be possible, the doublebonds must be aligned in very close proximity and with the correctgeometry. It is also necessary for several of these chains to be soaligned. The problem of ordering these systems to give layers withuniform properties is a difficult one and current approaches involve theuse of Langmuir-Blodgett troughs and thiol-metal anchors. The design andsynthesis of diacetylene molecules that can self-assemble to formstable, uniform 2-dimensional systems are important areas of endeavor.

There is an increasing amount of interest in the design of planarlamellar systems containing conjugated polydiacetylene functions. Thesesystems are known to display several interesting properties that couldlend themselves to the fabrication of a variety of devices (Okada, S.,et al., Acc. Chem. Res. 31:229-239 (1998); and Crooks, R. M., et al.,Acc. Chem. Res. 31:219-227 (1998)). For instance, they displaymechano-optical effects in which compressing the polydiacetylene layerslead to a change in color of the films (Nallicheri, R. A., et al.,Macromolecules 24:517-525 (1991); and Lovell, P. A., et al.,Macromolecules 31:842-849 (1998)). In other experiments, attaching acarbohydrate molecule to a polydiacetylene layer resulted in a change incolor when viral particles bound to the carbohydrate (Reichert, A., etal., J. Am. Chem. Soc. 117:829-830 (1995); and Spevak, W., et al., J.Am. Chem. Soc. 115:1146-1147 (1993)). Polydiacetylene layers alsodemonstrate color changes in response to alterations in temperature(Chance, R. R., et al., J. Chem. Phys. 71:206-211 (1979); Rubner, M. F.,et al., 20:1296-1300 (1987); and Wenzel, M., et al., J. Am. Chem. Soc.111:6123-6127 (1989)), pH (Mino, N., et al., Langmuir 8:594-598 (1992))and on exposure to some solvents (Nava, A. D., et al., Macromolecules23:3055-3063 (1990)). Polyacetylene is well recognized for its highelectrical conductivity. Unfortunately, it forms fibers not films, andits high insolubility and general physical intractability makes itunsuitable for many applications especially when lamellar systems aredesirable. Under favorable circumstances, the use of amphophilicmolecules with acetylene groups in the hydrocarbon chains leads to filmformation (Lio, A., et al., Langmuir 13:6524-6432 (1997) and Werkman, P.J., et al., Langmuir 14:157-164 (1998)). However, such molecules oftencontain only one hydrocarbon chain and they have a tendency to formmicellar systems. In order to obtain suitable films, the chains theneither have to be anchored to surfaces, or Langmuir-Blodget troughs haveto be employed (Charych, D. H., et al., Science 261:585-588 (1993);Berman, A., et al., Science, 269:515-518 (1995); Saito, A., et al.,Langmuir, 12:3938-3944 (1996); Deckert, A. A., et al., Langmuir,10:1948-1954 (1994); and Mowery, M. D., et al., Phys. Chem. B,101:8513-8519 (1997)). One serious problem with the ordering ofactylenic thiols on gold and other metal surfaces is the difficulty inensuring that the chains are aligned so that the alkyne groups are in aproper orientation and close enough to allow the polymerization process.This is difficult because imperfections on the metal surface of only afew atoms in dimension force adjacent chains to be at different heights,thus separating the acetylenic groups by too great a distance. Asubstrate-independent way of ordering alkyl chains with diacetylenicfunctions is therefore highly desirable. Molecular self-assembly hasmuch promise in this area.

Phospholipids readily form stable lamellar systems. The inclusion ofconjugated diacetylenic groups at the same position in each acyl chainof a phospholipid chain (FIG. 2) should give ideal self-assembling unitswhich can be polymerized to form highly organized, stable, 2-dimensionalsystems containing a conducting polydiacetylene layer. Unfortunately,the synthesis of phospholipids is extremely laborious. One approach thathas been tried is to use microorganisms to carry out the integration offatty acids containing diacetylenic functions into phospholipids. Usingthis strategy as much as 90% integration of diacetylenic fatty acidsinto microbial phospholipids was obtained (Leaver, J., et al., Biochim.Biophys. Acta 727:327-334 91983)). There are some problems with thisapproach however; because the membrane is only two molecules thick andjust surrounds the cell, the actual amount of material recovered pergram of cell mass is extremely small. In addition to this, the lipidspecies made by any one microorganism are extremely diverse and mayinclude neutral, and negatively charged headgroups with differentstructures. It is a challenge to separate species with only one type ofheadgroup and, even then, there is a tremendous amount of diversity inthe fatty acid species that are derived from the normal microbialmetabolism. Another disadvantage stems from the fact that microorganismscontain a myriad of membrane-associated enzymatic activities that canreduce or oxidize the diacetylenic functions. Because the microorganismsmake fatty acids de novo, it is very unlikely that any living systemexists that will incorporate only foreign fatty acids into its membranelipids.

Therefore, it is clear that only synthetic approaches have the potentialfor producing pure phospholipids or phospholipid analogs containingdiacetylenic functions in the fatty acyl chains and which have a highdegree of chemical integrity. Because of the difficulty in preparingphospholipids, simpler analogs which still contain the criticalstructural elements of phospholipids, a chiral 1,2-diacyl moiety and apolar headgroup, are desirable. Even more desirable are phospholipidanalogs that have the general structure of the lipids found in bacteriathat inhabit environments with extremely high temperatures or extremesof pH. The lipids of such organisms contain two transmembranehydrocarbon chains that are linked to a headgroup at either end. In somebacteria the linkages are ether linkages but in others (Lee, J., et al.,J. Am. Chem. Soc., 120:5855-5863 (1998); Jung, S., et al., J. Lipid Res.35:1057-1065 (1994)), they are ester functions (FIG. 2). Such moleculesshould self-assemble to form extremely stable lamellar systems withoutthe aid of devices such as Langmuir-Blodgett troughs. They would beexcellent targets for the preparation of planar polydiacetylenicsystems.

Objects

It is therefore an object of the present invention to provide novelpolyacetylene compounds and a process for the preparation thereof. It isfurther an object of the present invention to provide novelpolydiacetylene compounds which have unique properties. Further still,it is an object of the present invention to provide a process whichproduces the polyacetylenic compounds economically and in high purity.These and other objects will become increasingly apparent by referenceto the following description and the drawings.

SUMMARY OF THE INVENTION

The present invention relates to a process for producing an orderedpolyacetylene compound with two side-by-side carbon chains and alignedacetylene groups in each side chain. The process comprises reacting a1-N,N-dialkylaminoalkyl-3,4-dihydroxyalkyl amide with an acetylenecontaining acyl halide in a reaction mixture to produce1-N,N-dialkyamino-3,4-di(acetylenoxy group) alkylamide as the orderedpolyacetylene compound. In particular, the present invention relates toa process for producing an ordered polydiacetylene compound with twoside-by-side carbon chains and aligned diacetylene groups in each sidechain.

The present invention also relates to an ordered polyacetylene compoundwith two side-by-side carbon chains and aligned acetylene groups in eachchain which comprises 1-N,N-dialkyl amino alkyl-3,4-di(acetyleneoxygroup)alkylamide. In particular, the compound is an orderedpolydiacetylene compound with two side-by-side carbon chains and aligneddiacetylene groups in each chain which comprises 1-N,N-dialkyl aminoalkyl-3,4-di(acetyleneoxy group)alkylamide.

The present invention also relates to a film prepared from monomers ofthe polyacetylene. The film can be as a sheet or deposited on a surface.In the film the acetylene groups line up together across the sheet. Inparticular the film is prepared from monomers of polydiacetylene. Thepresent invention further relates to a process for preparing the filmfrom monomers of the polyacetylene, or in particular, monomers of thepolydiacetylene.

BRIEF DESCRIPTION OF DRAWINGS

FIGS. 1A, 1B and 1C are drawings showing the structures of compounds 1and 2 of the present invention and intermediate compound 3.

FIG. 2 is a drawing showing the structure of a typical phospholipid(phosphatidyl choline) containing diacetylenic fatty acyl groups knownto the prior art.

FIG. 3 is a drawing showing the structure of a membrane lipid from athermotropic bacterium known to the prior art.

FIG. 4 is a schematic drawing showing space filling models having theconformations of compounds 1 (left) and 2 (right) as indicated by NMRspectroscopy and molecular mechanics calculation. Black is oxygen ornitrogen. Small grey dots are hydrogen and large grey dots are carbon.

FIGS. 5A, 5B and 5C relate to atomic force microscopy (AFM) images. AFMimages of a film formed by compound 1 on a freshly-cleaned mica surface.FIG. 5A is a section analysis over a 4 μM length. FIG. 5B is a top viewof the same area as in FIG. 5A. FIG. 5C is a perspective surface plot ofthe same area as in FIG. 5B.

FIGS. 6A, 6B and 6C are AFM images of a film formed by compound 2 on afreshly-cleaned mica surface. FIG. 6A is a section analysis over a 2 μMlength. FIG. 6B is a top view of the same area as in FIG. 6A. FIG. 6C isa perspective surface plot of the same area as in FIG. 6B.

FIGS. 7A, 7B, 7C and 7D are laser scanning confocal micrographs ofhydrated films of compound 1 (7A) and compound 2 (7C). The images on theleft (FIGS. 7A, 7C) were acquired using cross polarizers and the imagesto the right (FIGS. 7B and 7D) were obtained using dark field optics.The films are the areas to the right of the fields.

FIGS. 8A and 8B are schematic drawings showing proposed packing modelsfrom compound 1 (FIG. 8A) and 2 (FIG. 8B) based on X-ray powderdiffraction information and molecular modeling.

FIGS. 9A to 9H are near infrared spectra of films formed from compound 1(FIGS. 9A to 9D) and compound 2 (FIGS. 9E to 9H). In A, B, E, F, thefilms were polymerized by UV irradiation and in C, D, G, H, the filmswere iodine doped. Spectra on the left were acquired in the range of600-1050 nm, and those to the right were acquired between 880 and 1700nm.

FIG. 10 is a drawing s howing the synthesis of compound 1.

FIG. 11 is a drawing showing the synthesis of compound 2.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to a process for producing an orderedpolyacetylene compound with two side-by-side carbon chains and alignedacetylene groups in each chain which comprises reacting a1-N,N-dialkylaminoalkyl-3,4-dihydroxyalkyl amide with an acyl halide ina reaction mixture to produce 1-N,N-dialkylamino-3,4-di(acetyleneoxygroup)alkylamide as the ordered polyacetylene compound, wherein alkyl inthe dialkyl amino is between 1 to 6 carbon atoms and acetyleneoxy groupis between 6 to 50 carbon atoms in a linear alkylene chain with theacetylene groups; and separating the ordered polyacetylene compound fromthe reaction mixture. In particular, to a process wherein the diacyldihalide is an acyl halide and the ordered polyacetylene compound hastwo alkyl amide groups positioned at each of the opposed ends of theacetylene dioxy group.

The present invention further relates to a process for producing anordered polydiacetylene compound with two side-by-side carbon chains andaligned diacetylene groups in each chain which comprises reacting a1-N,N-dialkylaminoalkyl-3,4-dihydroxyalkyl amide with an acyl halide ina reaction mixture to produce 1-N,N-dialkylamino-3,4-di(acetyleneoxygroup)alkylamide as the ordered polydiacetylene compound, wherein alkylin the dialkyl amino is between 1 to 6 carbon atoms and acetyleneoxygroup is between 6 to 50 carbon atoms in a linear alkylene chain withthe diacetylene groups; and separating the ordered polydiacetylenecompound from the reaction mixture. In particular, to a process whereinthe diacetylene oxyhalide is an diacyl dihalide and the orderedpolyacetylene compound has two alkyl amide groups positioned at each ofthe opposed ends of the diacetylene dioxy group.

In an embodiment further still, the present invention relates to aprocess for producing an ordered polydiacetylene compound with twoside-by-side chains and aligned diacetylene groups in each chain whichcomprises reacting a single chiral1-N,N-dimethylaminoethyl-3,4-dihydroxybutramide with an acyl halide in areaction mixture to produce 1-N,N-dimethyl amino-3,4-di(diacetyleneoxygroup)butyramide as the ordered polydiacetylene compound; and separatingthe ordered polydiacetylene compound from the reaction mixture. Inparticular to a process wherein the acyl halide is a diacyl dihalide andthe ordered polyacetylene has two alkylamide groups positioned at eachof the opposed ends of acetylene dioxy group.

The present invention relates to an ordered polyacetylene compound withtwo side-by-side carbon chains and aligned acetylene groups in eachchain which comprises 1-N,N-dialkyl amino alkyl-3,4-di(acetyleneoxygroup)alkylamide, wherein alkyl in the dialkyl amino is between 1 to 6carbon atoms and the acetyleneoxy group contains between 6 to 50 carbonatoms in a linear alkylene chain with the acetylene groups. Inparticular to the ordered polyacetylene compound wherein theacetyleneoxy group is an acetylene dioxy group and the orderedpolyacetylene compound has two alkyl amide groups positioned at each ofthe opposed ends of the acetylene dioxy group.

The present invention further relates to an ordered polydiacetylenecompound with two side-by-side carbon chains and aligned diacetylenegroups in each chain which comprises 1-N,N-dialkyl aminoalkyl-3,4-di(acetyleneoxy group)alkylamide, wherein alkyl in the dialkylamino is between 1 to 6 carbon atoms and polyacetylene contains between6 to 50 carbon atoms in a linear alkylene chain with the acetylenegroups. In particular, present invention relates to the orderedpolyacetylene compound wherein the acetyleneoxy group is an acetylenedioxy group and the ordered polyacetylene compound has two alkyl amidegroups positioned at each of the opposed ends of the acetylene dioxygroup.

The present invention relates further still to an orderedpolydiacetylene compound which comprises 1-N,N-dimethyl aminoethyl-3,4-di(diacetyleneoxy group) butyramide, wherein thediacetyleneoxy group is two linear alkylene chains with diacetylenegroups aligned in each chain. In particular, the present inventionrelates to the ordered polydiacetylene compound wherein thediacetyleneoxy group is a diacetylene dioxy group and the orderedpolyacetylene compound has an alkylamide group positioned at opposedends of the diacetylene dioxy group.

In a first embodiment of the present invention the compound has thestructure of compound 1 as shown in FIG. 1A. In the first embodimentcompound 1 is either (S) chiral or (R) chiral. In a second embodiment,the compound has the structure of compound 2 as shown in FIG. 2A and thecompound is either (S) chiral or (R) chiral. In a third embodiment, thecompound is compound 3 as shown in FIG. 1C and the compound is either(S) chiral or (R) chiral. Chirality of the polydiacetylene compoundsmade according to the present invention is a function of whether thepreferred 3-hydroxybutyrolactone is (S) chiral or (R) chiral.

The present invention also relates to a film prepared from monomers ofthe polyacetylene compound. The film can be cast as a sheet or depositedon a surface. In the film, the acetylene groups line up together acrossthe sheet. In a particular embodiment, the film is prepared from thepolydiacetylene compound. The present invention further relates to aprocess for preparing the film from the polyacetylene compound, or inparticular, the polydiacetylene compound.

Thus, the present invention relates to a film comprising monomers ofordered polydiacetylene with two side-by-side carbon chains and aligneddiacetylene groups in each chain which comprises 1-N,N-dialkyl aminoalkyl-3,4-di(acetyleneoxy group)alkylamide, wherein alkyl in the dialkylamino is between 1 to 6 carbon atoms and acetyleneoxy group containsbetween 6 to 50 carbon atoms in a linear alkylene chain with theacetylene groups assembled into a two-dimensional polymer structure. Ina specific embodiment, the acetyleneoxy group is an acetylene dioxygroup and the ordered polyacetylene compound has two alkyl amide groupspositioned at each of the opposed ends of the acetylene dioxy group.

The present invention also relates to a process for producing the filmof monomers of ordered polydiacetylene with two side-by-side carbonchains and aligned diacetylene groups in each chain which comprisesreacting a 1-N,N-dialkylaminoalkyl-3,4-dihydroxyalkyl amide with adiacetyleneoxyhalide in a reaction mixture to produce1-N,N-dialkylamino-3,4-di(acetyleneoxy group)alkylamide as the orderedpolydiacetylene compound, wherein alkyl in the dialkyl amino is between1 to 6 carbon atoms and acetyleneoxy group is between 6 to 50 carbonatoms in a linear alkylene chain with the diacetylene groups; separatingthe ordered compound from the reaction mixture; dissolving the compoundin a solvent; and depositing the dissolved compound on a substrate toform a two-dimensional structure. In a specific embodiment of theprocess, the acyl halide is a diacetylene dihalide and the orderedpolyacetylene compound has two alkyl amide groups positioned at each ofthe opposed ends of the diacetylene dioxy group.

The present invention further relates to a film composed of monomers ofordered polyacetylene with two side-by-side carbon chains and alignedacetylene groups in each chain which comprises 1-N,N-dialkyl aminoalkyl-3,4-di(acetyleneoxy group)alkylamide, wherein alkyl in the dialkylamino is between 1 to 6 carbon atoms and acetyleneoxy group containsbetween 6 to 50 carbon atoms in a linear alkylene chain with theacetylene groups to assemble a two-dimensional polymer structure. In aspecific embodiment, the acetyleneoxy group is an acetylene dioxy groupand the ordered polyacetylene compound has two alkyl amide groupspositioned at each of the opposed ends of the acetylene dioxy group.

The present invention also relates to a process for producing the filmof monomers of ordered polyacetylene with two side-by-side carbon chainsand aligned acetylene groups in each chain which comprises reacting a1-N,N-dialkylaminoalkyl-3,4-dihydroxyalkyl amide with an acyl halide ina reaction mixture to produce 1-N,N-dialkylamino-3,4-di(acetyleneoxygroup)alkylamide as the ordered polyacetylene compound, wherein alkyl inthe dialkyl amino is between 1 to 6 carbon atoms and acetyleneoxy groupis between 6 to 50 carbon atoms in a linear alkylene chain with theacetylene groups; separating the ordered polydiacetylene compound fromthe reaction mixture; dissolving the compound in a solvent; anddepositing the dissolved compound on a substrate to form thetwo-dimensional polymer structure.

The present invention further relates to a film of monomers of orderedpolydiacetylene which comprises 1-N,N-dimethyl aminoethyl-3,4-di(diacetyleneoxy group) butyramide, wherein diacetyleneoxy istwo linear alkylene chains with diacetylene groups aligned in each chainassembled into a two-dimensional polymer structure. In one embodiment ofthe invention, the diacetyleneoxy group is a diacetylene dioxy group andthe ordered polyalkylene compound has an alkylamide group positioned atopposed ends of the diacetylene dioxy group. In a specific embodiment ofthe invention, the acyl halide is an acyl dihalide and the orderedpolyacetylene compound has two alkyl amide groups positioned at each ofthe opposed ends of the acetylene dioxy group.

Finally, the present invention relates to a process for producing a filmof monomers of ordered polydiacetylene with two side-by-side chains andaligned diacetylene groups in each chain which comprises reacting asingle chiral 1-N,N-dimethylaminoethyl-3,4-dihydroxybutramide with anacyl halide in a reaction mixture to produce 1-N,N-dimethylamino-3,4-di(diacetyleneoxy group)butyramide as the orderedpolydiacetylene compound; separating the ordered polydiacetylenecompound from the reaction mixture; dissolving the compound in asolvent; and depositing the dissolved compound on a substrate to form atwo-dimensional structure. In a particular embodiment, the diacetyleneoxyhalide is a diacetylene dioxy halide and the ordered polyacetylenehas two alkylamide groups positioned at each of the opposed ends ofacetylene dioxy group.

In a first embodiment of a film of the present invention the monomercomprising the film has the structure of compound 1 as shown in FIG. 1A.In the first embodiment, the monomer is compound 1 which is either (S)chiral or (R) chiral. In a second embodiment, the monomer has thestructure of compound 2 as shown in FIG. 2A and the monomer is either(S) chiral or (R) chiral. In a third embodiment, the monomer is compound3 as shown in FIG, 1C and the monomer is (S) chiral or (R) chiral.Chirality of the polydiacetylene monomers made according to the presentinvention is a function of whether the preferred 3-hydroxybutyrolactoneis (S) chiral or (R) chiral.

Preparation of polyacetylenes according to the present inventionrequires a gamma-lactone (3-hydroxybutyrolactone), a reactant amide, anda reactant acetylene oxyhalide. The reactant amide can have the formula:

where R₁ and/or R₂ is a dialkyl aminoalkyl group, di-t-butyldicarbonate,formyl, acetyl or other blocking group. Preferred is thedimethylaminoethylene group in the intermediate compound 5 in FIG. 10where R₁ or R₂ is hydrogen.

The reactant acyl halide can have the formula:

wherein in n is 1 or 2, wherein at least one of R₃ or R₄ has a groupcomprising(CH₂)_(n), (CH═CH)_(n), (C═C)_(n), and (C═O)⁰⁻¹ wherein n isequal to or greater than 0, and wherein X₁ and/or X₂ which is reactivewith the hydroxyl groups of the amide and the other group X₁ or X₂ anon-reactive group or a reactive second group. FIG. 10 shows the productcompound 1 where X₁ and X₂ are chloride, so that a base can condense thehydroxyls of the amide with the chloride of the acetylene compound 6 byremoving hydrogen chloride. The acyl halide is prepared from thecorresponding acid reacted with an oxyacyl halide.

Typically the base is a Lewis base amine such as pyridine which reactswith the hydrogen chloride in a non-polar solvent, particularly ahalogenated solvent such as methylene dichloride.

The proper alignment of acyl chains can be obtained by the synthesis ofcompounds 1 and 2 (FIG. 1). Like typical phospholipids, they have twolong acyl chains preferably attached to a chiral 1,2-diol. They alsohave a dimethylaminoethane head blocking group. An important feature thetwo compounds have is that they are preferably chiral. When thediacetylenic units polymerize, chiral two dimensional polymers will beobtained. The synthesis of (S)-3-Hydroxy-γ-butyrolactone which was thesource of the chirality for compounds 1 and 2 has been described earlierin U.S. Pat. Nos. 5,374,773, 5,319,110, and 5,292,939 to Hollingsworthwhich are herein incorporated by reference. The synthetic routes areoutlined in FIGS. 10 and 11, respectively. Compounds 1 and 2 are newcompositions of matter.

Preparation of Compounds 1 and 2. The chiral, diacetylenic compounds 1and 2 were obtained in very good yield. In the case of 2 the preparationnecessitated only three steps all of which proceeded in good yield. Toprepare either compound 1 or 2 (Examples 2 and 3, respectively), onlythree steps were necessary, all of which proceeded in good yield. Thefirst step shown in Example 1 was reacting (S)-3-hydroxybutyrolactone(compound 4) with N,N-dimethylaminoethyl to produce theN,N-dimethylaminoethyl-3,4-dihydroxybutyramide (compound 5). The step toform compound 5 is essentially quantitative (FIG. 10). The second stepwas to make acetylene dioxyhalide compound 6 (FIG. 10) or acetyleneoxyhalide compound 7 (FIG. 11). This step is performed by reacting anacetyleneoxy with an oxalyl halide such as COCl₂ in an anhydrous solventsuch as dichloromethane. Finally, in the third step a compound 5 is witheither compound 6 or 7 in a condensation reaction to make compound 1 or2, respectively.

In the case of compound 1, the only possible complication was theformation of the isomeric structures in which the acyl chain was linkedto the primary hydroxyl group on one side and to the secondary group onthe other. This did not occur since only the intermediate compound 3(FIG. 1) in which a single chain was linked to the primary position ofan N-alkyl dihydroxybutyramide on each side was detected underconditions in which the reaction was only partially complete. Theidentity of the intermediate species as compound 3 was readilydetermined by ¹H-NMR and ¹⁴C-NMR spectroscopy. The signals for themethylene protons attached to oxygen appears at 4.30 and 4.10 ppmsubstantially downfield from their original positions in the startingdiol. The methine proton signal was not shifted from 4.06 ppm. Therewere no signals corresponding to un-esterified primary alcohols in thespectrum although a substantial degree of under-esterification of thesecondary position was evident from the spectra of the total mixture.

Supramolecular Structure, Stability, and Long-Range Order. Thesupramolecular structures of compounds 1 and 2 were determined by NMRspectroscopy (Examples 2 and 3, respectively). The parallel orientationof the two acyl chains of both compounds 1 and 2 was quite evident byNMR spectroscopy from the coupling constants of the methylene protonsattached to the acyloxy group. The coupling constants between theseprotons and the neighboring methine proton are indicative of therelative orientation of the acyloxy groups on these two carbons. Thesplittings were similar to those observed in a similar molecule wherethe acyl chains bore pyrenyl substituents at their termini and wereknown to be parallel by virtue of the fact that the pyrenyl groupsdisplayed excimer emission (Huang, G., et al., Tetrahedron 54:1355-1360(1998)). For compound 2, the signals for these methylene protons weretwo mutually coupled doublet of doublets. One appeared at 4.30 ppm (3.6Hz and 12.0 Hz) and the other at 4.12 ppm (5.8 Hz and 12 Hz). Thesevalues were also similar to those observed for the coupling constantsfor the 1 and 1′ protons with the 2-proton of the glyceryl moiety ofdiacyl glycerols. Similar results were observed for compound 1 althoughthe signals were considerably broadened in this case because of slowerrotational averaging in this latter system. The parallel nature of theacyl chains was also confirmed by X-ray diffraction analysis of thelipid systems in a water/alcohol system (Example 7). Reflections at 4.0Angstroms in the case of compound 2 and 3.4 Angstroms in the case ofcompound 1 were observed. These correspond to alkyl chain separationsand the smaller value of compound 1 was expected because in thismolecule, the chains are held together at both ends. These results inconjunction with molecular mechanics calculations supported theconformation of the molecules as shown in FIG. 4.

The long-range order of the 2-dimensional systems formed by compounds 1and 2 was examined by a combination of atomic force microscopy (AFM) andlaser scanning confocal microscopy using phase-contrast, dark field andpolarizing optics (Examples 5 and 6, respectively). As was mentionedearlier, X-ray analysis of the fully hydrated systems indicated that thehydrocarbon chains were arranged in a stacked parallel order as isexpected in lamellar systems. A reflection at 60 angstroms correspondingto slightly less than twice the width of a monolayer as measured fromthe molecular models was observed. This indicated that compound 2 formedslightly interdigitated bilayers. Atomic force micrographs (FIGS. 5A to5C and 6A to 6C) of layers of compounds 1 and 2 respectively prepared onmica plates demonstrated they formed flat films with a surface variationof only 9.85 nm over a distance of 1331 nm (0.7%) for compound 1, and 12nm over a 512 nm range (2.3%) for layer compound 2.

Information on the order and supramolecular organization of the twosystems was also obtained by analyzing images obtained from opticallaser scanning confocal microscopy. The most useful information wasobtained from images using polarizing optics. When using polarizingoptics, if the film layers are ordered relative to the plane of theslide and the polarized laser light is blocked by a cross polarizerafter going through the layer then only a black background is observed.However, if there are regions of disorder in the film, domains withinthe layer where the molecules are oriented differently or the layersbuckle, then the plane of polarization of the laser light is rotated andis no longer canceled by the cross-polarizing filter. Areas ofbrightness are then observed in these defective regions. As can be seenin FIGS. 7A and 7C for 1 and 2 respectively, the polarized lightmicrographs from both systems indicated a very high degree of order withonly a few point defects. The phase contrast images are shown in FIGS.7B and 7D. Significant defects were only observed at the edge of thelayers where there was a discontinuity or curvature as the film bent tocontact the glass.

Based on the 3-dimensional film structures proposed for compounds 1 and2, a packing model which is consistent with their long-range stabilityand high packing densities of these systems was derived. The model wasone that maximized the contact between the hydrocarbon chains such thatthe n-interaction was maximized and the alkane chains were in contactalong their entire length (FIGS. 8A and 8B). The n-overlap is expectedto be one of the dominant forces between the chains of these molecules.Based on the enthalpies of vaporization of a series of alkanes andconjugated and unconjugated diacetylenes (CRC Handbook of Physics andChemistry, CRC Press Boca Raton, Fla., U.S.A. (1997); and Mayer, E. S.,et al., J. Chem. Engin. Data 31:272-274 (1986)), this component wasestimated to be 5.1 Kcals per mole for chains just at the point ofseparating into the gas phase. This is a lower limit and a much highervalue is expected for closely packed chains. The dispersion forcesbetween methylene groups in hydrocarbons is an area that has obtainedmuch attention. of special importance has been the problem ofcalculating the dispersion energy between extended hydrocarbon chains inisolated molecules and large extended arrays (Salem, L., Can. J. ofBiochem. and Physiol. 40:1287-1298 (1962); and Jung, S., et al., J.Comp. Chem. 17:238-249 (1996)). In the case of compound 1 where thereare 16 methylene groups in contact and the chains are separated by 3.42Angstroms (based on the X-ray data) the total interaction energy is 45.2Kcals per mole. In the case of compound 2 where there are 20 methylenegroups in contact, but at a greater separation, this energy is expectedto be 31.5 Kcals per mole. This gives a lower limit for overallinter-chain interaction energies for compounds 1 and 2 of 50.3 and 36.6Kcals per mole, respectively. These values are substantially higher thanthe interaction energies of lipid molecules in biomembranes ofcomparable acyl chain length. In the case of compound 1, since thehydrocarbon chains are tethered at both ends, the average inter-chainseparation is even less. The attraction between the hydrocarbon chainsin this case is even greater since it is known to increase by two foldif the two chains move one Angstrom closer from a distance of 5Angstroms (Salem L., Can. J. of Biochem. and Physiol. 40:1287-1298(1962)). This dramatic increase in van der Waals energy with reducedchain separation will also be true for the n-stacking component which islikely to be severely underestimated here.

Formation, Characterization, and Properties of Polydiacetylene Films.Two methods were used to prepare materials with the desired optical andspectroscopic properties that are characteristic of conductivepolydiacetylene layers. Such conductive polydiacetylenic systems exhibitintense electronic transitions at long wavelengths. These electronictransitions go beyond the visible spectrum and well into the infraredregion. The optical properties of the polydiacetylenic systems madeaccording to the present invention were characterized by near IRspectroscopy experiments. The polydiacetylenic samples were prepared asdescribed in the Examples 2 and 3 and films prepared as in Example 4. IRspectra were measured over two ranges, from 600-1050 ηm and 900-1700 ηm.The results shown in FIGS. 9A to 9H show that the optical behavior ofthe two compounds polymerized by the same method are similar. Bothformed blue films on exposure to UV radiation. In the case of compound1, there was a strong absorption at 848.3 nm, and this extended to 1700nm. The maximum for UV-irradiated compound 2 appeared at 817.8 nm. Bothspectra displayed a small maximum at ˜700 nm. These polymerized bluefilms turned red on exposure to solvents such as chloroform. Films thatwere treated with iodine, were bright orange. The absorption maximum foriodine doped compound 1 appeared at 823.1 nm and the maximum forcompound 2 was at 772.8 nm. Again there was a small maximum at ˜700 nmin both spectra. The occurrence of such intense maxima in the region of800 nm and beyond with significant absorbance over 1600 nm in the filmsthat were prepared by this method is very unique. It is indicative ofthe extent of polymerization and demonstrates an exceptionally highlong-range order. Typically, no significant absorbance beyond 600-680 nmis observed in these systems (Okada, S., et al., Acc. Chem. Res.31:229-239 (1998); Charych, D. H., et al., Science, 261:585-588 (1993);Saito, A., et al., Langmuir, 12:3938-3944 (1996); and Huggins, K. E., etal., Macromolecules, 30:5305-5312 (1997)).

Preparation of gamma-lactone. An important precursor for preparingpolyacetylenes such as compound 1 or compound 2 is gamma-lactone(compound 4). Methods for making (S) 3,4-dihydroxybutanoic acid andcompound 4 therefrom by acidification with mineral oil can be found inU.S. Pat. Nos. 5,319,110, 5,374,773 and 5,292,939 to R. Hollingsworthwhich are herein incorporated by reference. U.S. Pat. Nos. 4,994,597 and5,087,751 to Inoue et al which also describes methods for making (S)3,4-dihydroxybutanoic acid are also hereby incorporated by reference.

An important feature of the present invention is that the synthesisprocess can produce either pure (R) or (S) chiral polyacetylenecompounds. The chirality of the polyacetylene compounds that aresynthesized is dependent on whether compound 4 is (R) or (S). Compound 4can be readily obtained from (R) or (S) 3,4-dihydroxybutanoic acid byacidification with mineral acid, and 3,4-dihydroxybutanoic acid can bereadily obtained by oxidation of sugars. The preparation of (S) isomersof 3,4-dihydroxybutanoic acid has been described in U.S. Pat. Nos.4,994,597, 5,087,751, 5,319,110, 5,292,939 and 5,374,773. Preparation of(R) isomers of gamma-lactone from (R) malic acid has been described byUchikawa et al., Bull. Chem. Soc. Jpn. 61: 2025-2029 (1988). However, aPatent Application to the inventor incorporated herein discloses thesynthesis of (R) or (S) isomers of 3,4-dihydroxybutanoic acid (I) fromsubstituted D- or L-pentoses. The process for the preparation of3,4-dihydroxybutanoic acid comprises reacting a mixture of a 3-leavinggroup substituted-n-pental (II) selected from the group consisting of2,4,5-trihydroxy-3-leaving group substituted-n-pental,2,4-dihydroxy-3-leaving group 4-0-protected substituted-n-pental,2-hydroxy-3-leaving group 4,5-di-O-protected substituted-n-pental,4-hydroxy-3-leaving group 2,5-di-O-protected substituted-n-pental,5-hydroxy-3-leaving group 2,4-di-O-protected substituted-n-pental, and3-leaving group 2,4,5-tri-O-protected substituted-n-pental with asolvent containing a peroxide in the presence of a base to produce (I)and a protonated leaving group, and then separating (I) from themixture. In this process, (I) can be produced by providing a substitutedpentose (III) selected from the group consisting of2,4,5-trihydroxy-3-R-pentose, 2,4-protected-3-R-pentose,4-protected-3-R-pentose, 2-protected-3-R-pentose, and5-protected-3-R-pentose in the reaction mixture wherein the substitutedpentose can be a leaving group substituted furanose (IV) or a leavinggroup substituted pyranose (V). In a preferred embodiment (I),(II),(III), (IV) and (V) are each a single chiral compound.

In making 3,4-dihydroxybutanoic acid, the peroxide is selected from thegroup consisting of hydrogen peroxide, alkaline earth peroxides, andcombinations thereof, and the base is selected from the group consistingof alkaline earths, alkaline metals, substituted ammonium hydroxides andcombinations thereof. The selection of the peroxide and the base is wellwithin the skill of the art. The solvent is selected from the groupconsisting of water and water miscible organic solvents, methanol,isopropanol, dioxane, tetrahydrofuran (THF), dimethylformamide andcombinations thereof. Hydrogen peroxide and sodium hydroxide have beenparticularly useful.

In the preparation of chiral 3,4-dihydroxybutanoic acid, the sodiumhydroxide or potassium hydroxide and the hydrogen peroxide molarconcentration is between 1 to 2 fold of the total pentose which usuallybetween 0.05% to 80% by weight per volume of the reaction mixture. Thereaction of the base with the pentose is preferably conducted for atleast 4 hours and preferably between 10 and 24 hours. Preferably, thereaction is conducted at a temperature between about 50° C. and 70° C.

The pentose is selected from the group consisting of D and L isomers.Examples of pentoses that can be used are arabinose, ribulose, xyloseand lyxose. In particular, the pentose can be a 3-leaving groupsubstituted pentose with a saccharide as the leaving group. Preferably,the pentose is selected from the group consisting of 3-O-methyl pentose,3-O-alkyl-pentose, 3,4-O-alkylidene-pentose, 3,5-O-alkylidene-pentose,2,3-O-alkylidene-pentose, 3,4-O-arylidene-pentose,3,5-O-arylidene-pentose, 2,3-O-arylidene-pentose, 3-O-acyl-pentose,3,4-O-acylidene-pentose, 2,3-O-acylidene-pentose,3,5-O-acylidene-pentose, ester-substituted-pentoses and 3-O-sugarsubstituted-pentose wherein the sugar provides the leaving group.

Furthermore, the leaving group is selected from the group consisting ofalkyloxy, aryloxy, acyloxy, halo, sulfonyloxy, sulfate, phosphate, and asaccharide and wherein (I), (II) and (IV) are each a single chiralcompound. Therefore, (I) is either an (R) isomer or an (S) isomer and ina preferred embodiment the pentose is selected from the group consistingof 3-O-methyl-arabinose, 3,4-O-methyl-arabinose,3,4-O-isopropylidene-arabinose, 3-O-galactopyranosyl-arabinose, and2,3-O-isopropylidene-arabinose. In a most preferred embodiment the2,4,5-trihydroxy-3-substituted-n-pentanal or other substituted pentoseor furanose is a D-sugar or a L-sugar. Thus, pentose sugars can beconverted to chiral 3,4-dihydroxybutanoic acid by oxidation with aperoxide source and a base if the pentose sugar is substituted at the3-position. The reaction proceeds by oxidation with a peroxide sourceand a base. As long as the 3-position is substituted, the substitutedsugar is converted to 3,4-dihydroxybutanoic acid.

The nature of the R group is quite variable. R can be any leaving groupexamples of which are alkyloxy, aryloxy, acyloxy, halo, sulfonyloxy,sulfate, or phosphate groups. The most easily obtained functionality isan alkoxy group. Hence 3-O-methyl pentoses are good substrates as arecertain acetals such as 3,4-O-isopropylidene, 3,5-O-benzylidene, and2,3-O-isopropylidene pentose acetals. Acyl and other ester substitutionsand disaccharides such as 3-O-β-D-galactopyranosyl-D-arabinose are alsouseful substrates. Thus, in addition to pentoses having 3-leavinggroups, pentoses having 3,4-leaving groups, 2,3-leaving groups and3,5-leaving groups are all encompassed by the present invention. Thedihydroxybutyric acid can be converted to the correspondinggamma-lactone by acidification with a mineral acid, concentrating andthen extracting the product into an organic solvent such asethylacetate, chloroform or tetrahydrofuran (THF). Thus, polyacetylenecompounds made according to the present invention can be eitherexclusively (R) or (S) when compound 4 is made from (R) or (S)3,4-dihydroxybutanoic acid.

In summary, the present invention describes compounds and processeswhich allowed the assembly of hydrocarbon chains containing diacetylenefunctions with the packing densities, orientation and long-range ordernecessary for forming highly conjugated 2-dimensional polymer systems.The present invention's strategy allows preparation of molecules whichare analogs of bio-membrane lipids and uses their self-assemblingpropensity to direct and achieve the regularity of packing and the high2-dimensional order that is required. The syntheses are characterized bybrevity and very high efficiency. A series of instrumental analysesindicated that these membrane lipid mimics of the present invention havethe desired properties; X-ray diffraction, laser confocal polarizedlight microscopy and molecular modeling all indicated that the compoundsof the present invention formed well oriented lamellar films. Atomicforce microscopy experiments further showed that very flat thin filmswere formed. Near IR study confirmed that the UV polymerized or dopedfilms have the desired optical properties. The conjugation wasexceptionally high with peak electronic transitions occurring way intothe infrared spectrum. Therefore, these membrane mimics have propertiesthat make them to be excellent building units for cast films. Anunexpected property of the compounds is that in the process of usingmonomers of the compounds to make films there is no need for an externalboundary to confine the monomers, the behavior of the system is builtinto the structure of the monomer. Therefore, the present inventionprovides a simple process for generating 2-dimensional molecular filmsor networks containing diacetylene functions. The present invention willhave important utility in the design of advanced materials andelectro-optical devices.

The following examples are intended to promote a further understandingof the present invention.

EXAMPLE 1

This example describes the synthesis of (S)1-N,N-dimethylaminoethyl-3,4-dihydroxybutyramide (compound 5). Thesynthetic route utilizes the stereocenter in (S)-3-hydroxybutyrolactone(compound 4) as the source of chirality for compounds 1 and 2. Thepreparation of the lactone has been described earlier in U.S. Pat. Nos.5,374,773, 5,319,110, and 5,292,939 to Hollingsworth which are hereinincorporated by reference.

The steps described herein have been demonstrated to preserve thestereocenter of the molecule (Huang, G., et al., Tetrahedron,54:1355-1360 (1998)). (S)-3-hydroxybutyrolactone 51 g (0.5 mol),N,N-dimethylethylenediamine 44 g (0.5 mol), and 100 ml absolute ethanolwere mixed and stirred for 24 hours. The solvent was removed by rotatoryevaporation under reduced pressure. The (S)1-N,N-dimethylaminoethyl-3,4-dihydroxybutyramide product was dried byvacuum oven for 24 hours to yield a heavy brown syrup 95 g (100%). ¹HNMR (300 MHZ, CDCl₃ δ6.19 (s (broad), 1H), 4.05 (m, 1H), 3.65 (dd, 1H,J=11.4, 3.9 Hz), 3.52 (dd, 1H, J=11.4, 5.1 Hz), 3.49-3.39 (m, 1H),3.33-3.21 (m, 1H), 2.45-2.35 (m, 4H), 2.23 (s, 6H). ¹³C NMR (75 MHZ,CDCl₃) 172.34, 69.12, 65.89, 57.83, 44.95, 39.60, 36.58. IR (NaClwindow, CHCl₃ as solvent), 3297, 3090, 2944, 2865, 2824, 2780, 1647,1555, 1462, 1190, 1040 cm⁻¹.

EXAMPLE 2

This example describes the preparation of compound 1 (FIG. 10). Allreactions and workups relating to diacetylenic compounds were conductedwith exclusion of light. Amber glassware was used and samples coveredwith aluminum foil. A photography safe light was used for illuminationwhen conducting chromatographic separations.

In the first step, 10,12-docosadiynedinoic and 1.81 g (0.005 mol),oxalyl chloride 15 ml (0.172 mol), and dry dichloromethane 10 ml, weremixed and stirred under a dry atmosphere overnight at room temperature.The solvent and excess oxalyl chloride were quickly removed underreduced pressure by rotatory evaporation. The diacyl dihydride product(compound 6) was taken up in 5 ml hexane and rotatory evaporated todryness to remove the last traces of oxalyl chloride.

The crude, freshly prepared (S)1-N,N-dimethylaminoethyl-3,4-dihydroxybutyramide (compound 5 madeaccording to Example 1) was used directly for the next reaction step. Amixture of dried compound 5 (0.95 g, 0.005 mol), 5 ml dry pyridine and 5ml of dry dichloromethane was cooled to oOC in an ice bath under drynitrogen. The acetylene dioxyhalide product (compound 6) was dissolvedin 5 ml of dry dichloromethane and added to the mixture of compound 5with a dropping funnel over a 10 minute period. The reaction mixture wasthen stirred for 24 hours. The solvent was removed by rotatoryevaporation and the residue taken up in chloroform. The dissolvedresidue was washed sequentially with 0.1 N HCl, saturated sodiumbicarbonate solution, and then brine. Then the organic phase was driedwith anhydrous sodium sulfate. Removal of the chloroform solvent yieldedas a red solid diacetylenic compound 1. The yield of compound 1 was 2.3g (89%) which was found to be homogeneous by thin layer chromatography.¹H NMR (300 MHZ, CDCl₃) 6.41 (s (broad), 2H), 5.40 (m, 2H), 4.31 (m,2H), 4.13 (m, 2H), 3.31 (m, 4H), 2.47 (m, 4H), 2.35-2.15 (m, 32H),1.64-1.40 (m, 16H), 1.27 (b, 32H) C¹³ NMR (75 MHZ, CDCl₃) 173.25,172.73, 168.63, 68.54, 65.20, 64.27, 57.53, 44.88, 37.82, 36.51, 34.17,33.98, 29.01, 28.86, 28.73, 28.24, 24.76, 19.12 IR (NaCl, CHCl₃) 2932,2855, 1738, 1653, 1547, 1462, 1159, 621.2 Fast atom bombardment massspectrometry (FABMS) 1033.9 (C₆₀H₉₆N₄O₁₀, NH⁺).

EXAMPLE 3

This example describes the preparation of compound 2 (FIG. 11). Themethod and workup were essentially the same as described above forcompound 1 with slight differences in procedure.

In the first step, 10,12-pentacosadynoic acid (2.24 g, 0.006 mol), 10 mloxalyl chloride (0.115 mol) and dry dichloromethane 10 ml were stirredovernight at room temperature. The solvent and excess oxalyl chloridewere quickly removed under reduced pressure by rotatory evaporation. Theacetylene oxyhalide product (compound 7) was taken up in 5 ml hexane androtatory evaporated to dryness to remove the last traces of oxalylchloride.

For the esterification,(S)1-N,N-dimethylaminoethyl-3,4-dihydroxybutyramide (compound 5) 0.475 g(0.0025 mol) was used for the reaction. A mixture of dried compound 5, 5ml dry pyridine and 5 ml of dry dichloromethane was cooled to 0° C. inan ice bath under dry nitrogen. The acetylene oxyhalide product(compound 7) was dissolved in dry dichloromethane and added to themixture of compound 5. The reaction mixture was then stirred for 24hours. The crude product was purified by flash column chromatography onsilica gel using chloroform:acetone:methanol (1:1:1) as the solvent. Thediacetylenic compound 2 was obtained as a purple solid 1.97 g (87%) ¹HNMR, (300 MHZ, CDCl₃) 6.92 (s, 1H), 5.39 (m, 1H), 4.30 (dd, 1H, J=3.6,12.0 Hz) 4.12 (dd, 1H, J=5.8, 12 Hz) 5.35 (m, 2H), 2.55-2.44 (m, 2H),2.32-2.18 (m, 24H), 1.64-1.42 (m, 12H), 1.40-1.10 (m, 2H), 0.85 (t,J=6.6 Hz). ¹³C NMR (75 MHZ, CDCl₃), 173.30, 172.78, 168.90, 68.58,65.27, 65.18. 64.38, 57.52, 44.50, 37.75, 36.20, 34.23, 34.03, 31.89,29.61, 29.46, 29.33, 29.09, 28.91, 28.85, 28.78, 28.33, 24.80, 22.67,19.18, 14.11. IR (NaCl, CHCl₃) 2919, 2851, 1734, 1653, 1470, 1246, 1175,718. cm⁻¹. FABMS 903.7 (MH⁺, C₅₈H₉₈N₂O₅). Because of their high labilityto oxygen and instability to light combustion, analyses could not beobtained on these materials.

EXAMPLE 4

This example describes making films using compound 1 or 2 and analyzingthe properties of the films thus formed by infrared (IR) spectroscopy.

Compound 1 or 2 was dissolved in chloroform to give an approximately 1%solution. A few drops of the clear solution was transferred by a Pasteurpipette onto clean microscope slides. The solution which spread acrossthe slide, evaporated leaving behind a film layer. The film was eitherpolymerized by irradiation with UV light (254 nm, 6 Watts, 350 μWattsper cm² for 3 minutes) or the film layer was doped by holding the slidein a horizontal position about 10-15 cm above some iodine crystals atroom temperature. In the UV polymerization experiment, the light yellowto colorless film turned to blue after UV irradiation. In contrast, thefilms turned yellow-orange after doping with iodine.

Near IR experiments were performed using diode array spectrometers fromControl Data (South Bend, Ind.). The films were irradiated using atungsten source and the slides were placed directly in the light path.FIGS. 9A to 9H are near IR spectra of films formed from compound 1(FIGS. 9A to 9D) and compound 2 (FIGS. 9E to 9H). In A, B, E, F, thefilms were polymerized by UV irradiation and in C, D, G, H, the filmswere iodine doped. Spectra on the left were acquired in the range of600-1050 nm, and those to the right were acquired between 880 and 1700nm.

The near IR results show that compounds 1 or 2 polymerized as shownabove have optical properties that are desirable and similar.

EXAMPLE 5

This example demonstrates formation of films of either compound 1 or 2and the properties of the films thus formed using atomic forcemicroscopy (AFM). The AFM analyses were performed using a Nanoscope IIIinstrument which was operating in contact mode. For these measurements,compound 1 or 2 were dissolved in chloroform-methanol (0.5-1% solutions)and ˜10 μL was transferred to freshly cleaved mica plates spinning at200 rpm. The rotation of the mica plates facilitated even film spreadingand evaporation.

FIGS. 5A, 5B and 5C show AFM images of a film formed by compound 1 on afreshly-cleaned mica surfaces. FIG. 5A shows a sectional analysis of thefilm conducted over a 4 μM length. FIG. 5B is a top view of the samearea shown in FIG. 5A. FIG. 5C is a perspective surface plot of the samearea shown in FIG. 5B. FIGS. 6A, 6B and 6C are AFM images of a filmformed by compound 2 on a freshly-cleaned mica surface. FIG. 6A shows asectional analysis of the film conducted over a 2 μM length. FIG. 6Bshows a top view of the same area shown in FIG. 6A. FIG. 6C is aperspective surface plot of the same area shown in FIG. 6B.

The AFM analysis showed that the films were very flat and thin. Inparticular, compound 1 had a surface variation of only 9.85 nm over adistance of 1331 nm (0.7%) and compound 2 had a surface variation of 12nm over a distance of 512 nm (2.3%).

EXAMPLE 6

This example demonstrates formation of films of either compound 1 or 2and the properties of the films thus formed using Laser scanningconfocal light microscopy. These experiments were performed on a Zeiss210 instrument with a 488 nm laser. Images were obtained in the brightfield, dark-field, phase contrast and polarization modes. For thepolarizing mode experiments, an analyzing cross-polarizer was placed onthe objective lens and rotated until light cancellation. For filmpreparation, compound 1 or 2 was dissolved in a 4:1 ethanol:watermixture, and a few drops of solution were deposited on clean glassslides which were left in a horizontal position at 30-40° C. for twohours to allow the solvent to evaporate.

FIGS. 7A, 7B, 7C and 7D are laser scanning confocal micrographs ofhydrated films of compound 1 (7A and 7B) and compound 2 (7C and 7D). Theimages on the left (FIGS. 7A, 7C) were acquired using cross polarizersand the images to the right (FIGS. 7B and 7D) were obtained using darkfield optics. The films are the areas to the right of the fields. Theseresults show that films composed of either compound 1 or 2 were highlyordered structures, with only a few point defects. The only significantdefects were found at the fringes of the films which was because of theedges of the films were bent in contact with the glass.

EXAMPLE 7

This example demonstrates formation of films of either compound 1 or 2and the properties of the films thus formed using X-ray diffraction.These studies were performed on a Rigaku instrument with a Rotaflexrotating copper anode operating at 45 kV with a current of 100 mA. TheX-ray beam was collimated with a 1/6 slit and the Kα line was selected.Compound 1 or 2 was dissolved in a minimum volume of ethanol and 1/4 to1/3 the volume of water added so that an overall 20% cloudy but uniformdispersion of sample was obtained. The samples were sonicated andvortexed several times to ensure uniformity of distribution and thensealed in glass capillaries and diffraction data obtained.

X-ray powder diffraction information for compounds 1 and 2 was used tomake molecular models for films comprised of either compound which areshown in FIG. 8.

EXAMPLE 8

Molecular Mechanics Calculations of compounds 1 and 2 and films composedof compounds 1 or 2 were performed using the MM3 forcefield (Allinger,N. L., et al., J. Amer. Chem. Soc. 111:8551-8566 (1989)) as implementedin the program Alchemy (Tripos, Inc., St. Louis, Mo. 63144 USA).Minimizations were performed using the conjugate gradient method. Theparameters were used without modification since the MM3 forcefield isparametized to very accurately reproduce the geometries and heats offormation of hydrocarbons.

EXAMPLE 9

This example shows various methods for preparing compound 4 which iseither (R) chiral or (S) chiral using substituted pentose sugars.

Preparation of (R) -3-hydroxy-γ-butyrolactone.3,4-O-isopropylidene-L-arabinose (30 grams) was treated with 2700 ml of0.36% sodium hydroxide and 27 grams of 30% hydrogen peroxide. Themixture was heated at 65° C. for 10 hours. Afterwards, the reaction wasextracted with one volume of ethyl acetate, concentrated to a syrup andacidified to pH 1 with 6 M sulfuric acid, and the acidified syrupconcentrated at 40° C. until no more solvent was removed. Then the syrupwas extracted with 1.5 liters of ethyl acetate. The ethyl acetate layerwas concentrated to yield 15.5 grams (96%) of(R)-3-hydroxy-γ-butyrolactone. The product was greater than 90% pure asjudged by gas chromatography. Chiral GC analysis on a cyclodextrin phaseshowed that there was greater than 99.8% of the(R)-3-hydroxy-γ-butyrolactone product.

Preparation of (R)-3-hydroxy-γ-butyrolactone using3,4-O-methyl-L-arabinose. 3,4-O-methyl-L-arabinose (30 grams) wastreated with 2700 ml of 0.36% sodium hydroxide and 27 grams of 30%hydrogen peroxide. The mixture was heated at 65° C. for 10 hours.Afterwards, the reaction was extracted with one volume of ethyl acetate,concentrated to a syrup and acidified to pH 1 with 6 M sulfuric acid,and the acidified syrup concentrated at 40° C. until no more solvent wasremoved. Then the syrup was extracted with 1.5 liters of ethyl acetate.The ethyl acetate layer was concentrated to yield 95%(R)-3-hydroxy-γ-butyrolactone. The product was greater than 95% pure asjudged by gas chromatography. The optical purity was greater than 99.8%.

Preparation of (S) -3-hydroxy-γ-butyrolactone using3-O-β-D-galactopyranosyl-D-arabinose.3-O-β-D-galactopyranosyl-D-arabinose (30 grams) was treated with 2700 mlof 0.36% sodium hydroxide and 27 grams of 30% hydrogen peroxide. Themixture was heated at 65° C. for 10 hours. Afterwards, the reaction wasextracted with one volume of ethyl acetate, concentrated to a syrup andacidified to pH 1 with 6 M sulfuric acid, and the acidified syrupconcentrated at 40° C. until no more solvent was removed. Then the syrupwas extracted with 1.5 liters of ethyl acetate. The ethyl acetate layerwas concentrated to yield 85% (R)-3-hydroxy-γ-butyrolactone. The productwas greater than 90% pure as judged by gas chromatography. The opticalpurity was greater than 99.8%.

Preparation of (S) -3-hydroxy-γ-butyrolactone using2,3-O-isopropylidene-D-arabinose. 2,3-O-isopropylidene-D-arabinose (30grams) was treated with 2700 ml of 0.36% sodium hydroxide and 27 gramsof 30% hydrogen peroxide. The mixture was heated at 65° C. for 10 hours.Afterwards, the reaction was extracted with one volume of ethyl acetate,concentrated to a syrup and acidified to pH 1 with 6 M sulfuric acid,and the acidified syrup concentrated at 40° C. until no more solvent wasremoved. Then the syrup was extracted with 1.5 liters of ethyl acetate.The ethyl acetate layer was concentrated to yield 60%(S)-3-hydroxy-γ-butyrolactone. The product was greater than 85% pure asjudged by gas chromatography. The optical purity was greater than 99.8%.

While the present invention is described herein with reference toillustrated embodiments, it should be understood that the invention isnot limited hereto. Those having ordinary skill in the art and access tothe teachings herein will recognize additional modifications andembodiments within the scope thereof. Therefore, the present inventionis limited only by the Claims attached herein.

We claim:
 1. An intermediate compound of the formula:


2. The compound of claim 1 which is (S) chiral.
 3. The compound of claim1 which is (R) chiral.